EP2038452B1 - Procédé destiné à la fabrication d'une surface superhydrophobe - Google Patents

Procédé destiné à la fabrication d'une surface superhydrophobe Download PDF

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Publication number
EP2038452B1
EP2038452B1 EP07768622.8A EP07768622A EP2038452B1 EP 2038452 B1 EP2038452 B1 EP 2038452B1 EP 07768622 A EP07768622 A EP 07768622A EP 2038452 B1 EP2038452 B1 EP 2038452B1
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EP
European Patent Office
Prior art keywords
metal body
scale
nano
depressions
micro
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
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EP07768622.8A
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German (de)
English (en)
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EP2038452A1 (fr
EP2038452A4 (fr
Inventor
Woon-Bong Hwang
Kun-Hong Lee
Hyun-Chul Park
Dong-Hyun Kim
Joon-Won Kim
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Academy Industry Foundation of POSTECH
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Academy Industry Foundation of POSTECH
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F17/00—Multi-step processes for surface treatment of metallic material involving at least one process provided for in class C23 and at least one process covered by subclass C21D or C22F or class C25
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/006—Nanostructures, e.g. using aluminium anodic oxidation templates [AAO]
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/10—Moulds; Masks; Masterforms
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/24—Chemical after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
    • Y10T428/24612—Composite web or sheet

Definitions

  • the present invention relates to a method of processing a superhydrophobic surface. More particularly, the present invention relates to a surface processing method using a surface treatment of a metal body and a replication process.
  • a surface of a solid body formed of metal or polymer has inherent surface energy.
  • the inherent surface energy is represented as a contact angle between liquid and a surface of a solid body when the liquid contacts the surface of the solid body.
  • a spherical drop of liquid loses its shape to change into hydrophilicity wetting the surface of the solid body.
  • the contact angle is greater than 90 °, the spherical drop maintains its spherical shape to have hydrophobicity that does not wet the solid body but easily flows.
  • the hydrophobicity of the drop can be noted from a case where a drop of water falling on a lotus leaf does not wet the lotus leaf but flows along a surface of the leaf.
  • the inherent contact angle of the surface of the solid body may be varied by processing the surface such that the surface has protrusions and depressions. That is, the hydrophilicity of the surface having the contact angle less than 90 ° may be further enhanced through a surface treatment process. Likewise, the hydrophobicity of the surface having the contact angle greater than 90 ° may be also further enhanced through the surface treatment process.
  • the hydrophobicity surface of the solid body may be used for a variety of following applications. That is, the hydrophobicity surface can be applied to a condenser of an air conditioning system to enhance the condensing efficiency. When the hydrophobicity surface is applied to a drink can, the residue can be completely removed from the can and thus the recycling process of the can may be simplified.
  • the hydrophobicity surface when the hydrophobicity surface is applied to a window glass of a vehicle, it can prevent the window glass from being steamed up when there is a difference between an indoor temperature and an outdoor temperature.
  • the hydrophobicity surface When the hydrophobicity surface is applied a ship, the ship can show a higher impellent force using the same power.
  • the hydrophobicity surface when the hydrophobicity surface is applied to a dish antenna, it can prevent snow from covering a surface of the dish antenna.
  • the hydrophobic surface is applied to a water supply pipe, the water flow rate can be improved.
  • MEMS microelectromechanical system
  • Exemplary embodiments of the present invention provide a method for processing a superhydrophobic surface, which can reduce the processing cost by mass-produce-processing the hydrophobic surface through a simple process.
  • a method of processing a superhydrophobic surface includes i) orienting a spray nozzle of a particle sprayer toward a surface of a metal body, ii) operating the particle sprayer to forming micro-scale protrusions and depressions on the surface of the metal body by spraying particles to the surface of the metal body, iii) forming a plurality of nano-scale holes on the surface of the metal body by treating the metal body through an anodic oxidation process, iv) forming a replica by immersing the metal body in a non-wetting polymer material and solidifying the non-wetting polymer material, and v) forming a superhydrophobic dual-scale surface structure having nano-scale pillars formed on micro-scale protrusions and depressions by removing the metal body and an anodic oxide from the replica.
  • the diameter of the particle used for particle sprayer is in the range from 50 ⁇ m to 180 ⁇ m.
  • the diameter of the nano-scale hole is in the range from 35 nm to 200 nm.
  • the aspect ratio of the nano-scale hole may be in the range from 3 to 10, more preferably, in the range from 5 to 7.5.
  • the non-wetting polymer material may be selected from the group consisting of PTFE (Polytetrahluorethylene), FEP (Fluorinated ethylene propylene copoymer), PFA (Perfluoroalkoxy), and a combination thereof.
  • PTFE Polytetrahluorethylene
  • FEP Fluorinated ethylene propylene copoymer
  • PFA Perfluoroalkoxy
  • the metal body may be formed of an aluminum or aluminum alloy.
  • the particle sprayer may be a sand blaster spraying sand particles.
  • the particle sprayer may be designed to spray metal particles.
  • micro-scale size is defined as a size in the range equal to or more than 1 ⁇ m and less than 1000 ⁇ m
  • nano-scale size is defined as a size in the range equal to or more than 1nm and less than 1000nm.
  • a surface processing apparatus of a solid body includes a particle sprayer 10 for forming micro-scale protrusions and depressions on a surface of a metal body 13, an anodic oxidation apparatus 20 for performing an anodic oxidation process on the surface of the metal body 13, and a replication apparatus 30 for performing a replication process for forming a duplication corresponding to a surface shape of the metal body 13 by immersing the metal body 13 in a non-wetting material 32.
  • the particle sprayer 10 sprays particles 11 with a predetermined speed and pressure so that the particles 11 collide with the surface 13a of the metal body 13.
  • the surface 13a of the metal body receives impact energy by the collision with the particles 11 and thus the surface 13a of the metal body 13 is deformed.
  • the particle sprayer 10 may be, for example, a sand blaster spraying sand particles.
  • the particle sprayer 10 may be designed to spray metal particles.
  • the metal body may be provided in the form of a metal plate formed of aluminum, steel, copper, and the like.
  • the diameter of the particle used for the particle sprayer 10 may be in the range from 50 ⁇ m to 180 ⁇ m.
  • FIG. 2 is a perspective view of a metal body having a surface provided with micro-scale protrusions and depressions produced by the method of the present invention. In FIG. 2 , a portion of the surface is enlarged and illustrated by a section.
  • a height of each of the protrusions 15a, a depth of each of the depressions 15b, and a distance between the protrusions 15a, and the like may be varied in accordance with a particle spraying speed and pressure of the particle sprayer 10 and a size of the particle. These parameters may be preset properly.
  • a normal solid such as metal or polymer is a wetting material having a contact angle of 90°.
  • FIG. 3 is a schematic diagram of an anodic oxidation apparatus, illustrating an anodic oxidation process.
  • the anodic oxidation apparatus 20 includes a main body 21 provided with a receiving space for receiving the metal body 13, electrolyte solution 23 stored in the main body 21, and a power source 25 for supplying cathode and anode voltages to the metal body 13.
  • the electrolyte solution 23 is stored in a storing space of the main body 21.
  • the metal body 13 is received in the storing space.
  • the metal body 13 is formed of a conductive material such as aluminum.
  • a pair of the main bodies 13a and 13b are provided.
  • other conductive materials to which electric power can be applied may be used for the metal body.
  • One of the metal bodies 13a and 13b is applied with the anode voltage from the power source 25 and the other is applied with the cathode voltage from the power source 25. By doing this, an anodic oxidation process for forming nanometer-sized holes on the surface of the metal body 13 is performed.
  • the metal body 13 is immersed in the electrolyte solution 23 contained in the main body 21.
  • sulfuric acid, phosphoric acid or oxalic acid may be selectively used as the electrolyte solution 23 for the anodic oxidation process.
  • one of the solid bodies 13a and 13b is applied with the anode voltage from the power source 25 and the other is applied with the cathode voltage from the power source 25. Therefore, as shown in FIG. 4 , an anode oxide portion 14 is formed on the surface of the metal body 10.
  • alumina that is an oxide layer is formed on the surface of the metal body 10.
  • Nano-scale holes 17 each having a nano-scaled diameter are formed in the anodic oxide portion 13.
  • the diameter and depth of the nano-scale hole 17 may be controlled by selecting the electrolyte solution and controlling the applied voltage used for anodizing process.
  • the diameter of the nano-scale hole 17 may be in the range from 35 to 200 nm.
  • the surface of the metal body 13 is provided with the micro-scale protrusions 15a and depressions 15b that are formed through a process using the particle sprayer 10 as well as the holes 17 that are formed through the anodic oxidation process and have a nanometer-sized diameter.
  • FIGS. 6A and 6B are SEM images of the surface of the metal body that is provided with the nano-scale holes that are formed through an anodic oxidation process. It can be noted from FIGS. 6A and 6B that the holes 17 each having a nanometer-sized diameter are formed in the surface of the metal body 13.
  • the metal body 13 that are processed by the particle sprayer and the anodic oxidation process are loaded in the replication apparatus 30.
  • the replication apparatus includes a main body 31, a receiving portion 33 that is formed in the main body to receive the metal body 13 and non-wetting polymer solution 32, and a cooling unit 35 that is arranged along a side of the main body 31 to solidify the non-wetting polymer solution 32.
  • the metal body 13 and the non-wetting polymer solution 32 are received in the receiving portion 33.
  • the non-wetting polymer solution 32 may be selected from the group consisting of polytetrahluorethylene (PTFE), fluorinated ethylene propylene copolymer (PEF), perfluoroalkoxy (PFA), and a combination thereof.
  • PTFE polytetrahluorethylene
  • PEF fluorinated ethylene propylene copolymer
  • PFA perfluoroalkoxy
  • the non-wetting polymer solution 32 is solidified to surround the metal body 13 in the receiving portion 33. In order to easily solidify the non-wetting polymer solution 32, cooling water flows along the cooling unit 35.
  • a hydrophobic polymer replica 18 is formed as shown in FIGS. 9A to 9F . That is, when the non-wetting polymer solution is solidified in a state where the metal body 13 is immersed therein, the hydrophobic polymer replica 18 having a shape corresponding to a shape of the surface of the metal body 13 can be formed.
  • the metal body 13 and the anodic oxide portion 14 are removed from the hydrophobic polymer replica 18.
  • the metal body 13 is formed of aluminum and thus the anodic oxide portion is the alumina, the metal body and the alumina can be removed through a wet-etching process. Accordingly, replication of a surface shape of the metal body 13 is realized on the surface of the hydrophobic polymer replica 18, thereby making it possible to form a polymer solid body 19 having a superhydrophobic surface with minimum wettability.
  • the surface of the polymer solid body 19 is provided with micro-scale protrusions 15a and depressions 15b as well as a plurality of nano-scale pillars 19b each having a diameter identical to that of the nano-scale hole 17, such that the polymer solid body 19 has a surface of dual-scale structures.
  • the diameter of the nano-scale pillar 19b is in the range from 35 to 200 nm, since the diameter of the nano-scale hole 17 is in the range from 35 to 200 nm. Accordingly, the diameter ratio of micro-scale protrusions and depressions 15 to nano-scale pillars 19b formed on the surface of the solid body 19 is in the range from 250 to 5140, since the diameter of the particles sprayed from the particle sprayer 10. When the diameter ratio is less than 250, the micro-scale protrusions and depressions are unduly dominant over the nano-scale pillars such that dual-scale structure is not represented on the surface of the solid body. When the diameter ratio is more than 5140, the micro-scale protrusions and depressions and the nano-scale pillars become similar size such that dual-scale structure is not represented on the surface of the solid body.
  • the aspect ratio of the nano-scale hole 17 may be in the range from 3 to 10, more preferably, in the range from 5 to 7.5.
  • the aspect ratio of the nano-scale hole 17 depends on the anodizing time. When the aspect ratio is less than 3, the characteristic of the nano-scale pillar replicated from the nano-scale hole 17 is weak and the micro-scale protrusions and depressions are unduly dominant over the nano-scale pillars such that dual-scale structure is not represented on the surface of the solid body. When the aspect ratio is more than 10, the nano-scale pillars are stuck to each other due to adhesive force by van der Waals' interaction thereby counterbalancing the characteristic of the micro-scale protrusions and depressions.
  • the polymer solid body 19 includes a base 19a formed on at least partly the surface thereof and provided with the micro-scale protrusions and depressions.
  • the protrusions 19b each having a nanometer-sized diameter are formed on the base.
  • the protrusions 19b are formed of a non-wetting polymer material.
  • the non-wetting polymer material may be selected from the group consisting of polytetrahluorethylene (PTFE), fluorinated ethylene propylene copolymer (PEP), perfluoroalkoxy (PFA), and a combination thereof.
  • FIGS. 10A and 10B are SEM images of the solid body having the superhydrophobic surface.
  • FIGS. 9A through 9D are views illustrating a method of processing a replica according to an exemplary embodiment of the present invention.
  • FIGS. 9A to 9F The following will describe a method of processing a replica with reference to FIGS. 9A to 9F .
  • like reference numerals indicate like parts.
  • a spray nozzle 12 of the particle sprayer 10 is oriented toward the surface 13a of the metal body 13.
  • the particle sprayer 10 is operated to spray the particles 11 to the surface of the metal body 13. Then, as shown in FIG. 9B , the micro-scale protrusions and depressions are formed on the surface of the metal body 13 as the particles 11 collide with the surface.
  • the surface of the metal body 13 on which the micro-scale protrusions and depressions are formed is treated through an anodic oxidation process.
  • the nano-scale holes 17 are formed on the surface of the metal body 13. Therefore, the surface of the metal body 13 is provided with the micro-scale protrusions 15a and depressions 15b that are formed through a process using the particle sprayer 10 as well as the nano-scale holes 17 that are formed through the anodic oxidation process.
  • the metal body 13 is immersed into the non-wetting material 32 and the non-wetting material 32 is solidified. As the non-wetting material 32 is solidified and changes to the hydrophobic polymer replica 18 is formed.
  • the protrusions 19b each having a diameter identical to the nano-scale diameter of each of the holes 17 formed on the surface of the metal body 13 are formed on the surface of the hydrophobic polymer solid body 19. Therefore, the polymer solid body 19 having the superhydrophobic surface can be realized.
  • the next step is anodization, which was carried out in 0.3 M oxalic acid solution.
  • the sandblasted aluminum sheet was used as the anode, and a flat platinum sheet as the cathode.
  • the electrodes were about 5 cm apart.
  • a potential difference of 40 V DC was applied by a computer-interfaced power supply (Digital Electronics Co., DRP-92001DUS).
  • the sandblasted aluminum sheet was anodized for 4 minutes. During anodization the solution was maintained at a temperature of 15° C by a circulator (Lab. Companion, RW-0525G).
  • the next step is the replication.
  • the nano-scale honeycomb structure (anodic aluminum oxide, AAO) was used as the template material.
  • the dipping method was used with the mixed solution of PTFE (0.3 wt%) and the solvent, which comprises a solution of 6 wt% PTFE (Polytetrafluoroethylene, DuPont Teflon® AF: Amorphous Fluoropolymer Solution) in the solvent (ACROS, FC-75).
  • PTFE Polytetrafluoroethylene
  • DuPont Teflon® AF Amorphous Fluoropolymer Solution
  • the final step is removal of the nano-scale honeycombe template (AAO template).
  • AAO template nano-scale honeycombe template
  • the aluminum layer was removed in HgCl 2 solution. Residual porous alumina was then removed in a mixture of 1.8 wt% chromic acid and 6 wt% phosphoric acid at 65 °C for 5 hours.
  • the sessile drop method which measures the contact angle (CA) of a water droplet on a surface, was used to characterize the wetting properties of the resulting micro/nanostructures.
  • a surface analyzer, DSA-100 (Krüss Co.) was used for the measurement.
  • Steady-state contact angles were measured using a 4 ⁇ L deionized water droplet. At least five different measurements were performed on different areas of each specimen at room temperature.
  • FIG. 11 (a) is a SEM image representing a surface of the untreated normal industrial aluminum
  • FIG. 11(b) is a SEM image representing micro-scale protrusions and depressions of a sandblasted surface of aluminum
  • FIG. 11(c) is a SEM image representing an anodized surface of porous anodic alumina after sandblasting.
  • the anodizing was carried out at 40 V in a 0.3 M oxalic acid solution at 15°C for 4 minutes.
  • the surface exhibits nano-scale hole (about 40 nm) structures with micro-scale random roughness on the alumina surface.
  • the depth of the hole is about 350 nm, and the distance between the neighboring holes is 100 nm.
  • This anodizing process altered the sandblasted aluminum surface to the porous alumina surface, which exhibits hierarchical structures, having nanostructures on microstructures.
  • FIG. 12 (a) is a SEM image of sandblasted PTFE replica
  • FIG. 12(b) is a SEM image of superhydrophobic PTFE replica replicated from the anodic aluminum oxide template being anodized after sandblasting.
  • No nano-scale pillars exist in FIG. 12(a) but are present in FIG. 12 (b) .
  • the length of the pillars is about 300 nm.
  • FIG. 13 shows measured values of the contact angle.
  • the contact angle of the sandblasted PTFE replica surface is 135° , as shown in FIG. 13(a) .
  • the intrinsic contact angle of PTFE is 120° , so that the microscale roughness of the surface increases the hydrophobicity.
  • the sandblasted porous alumina PTFE replica surface has a contact angle of 165° ( FIG. 13(b) ). These were average values of the measured contact angle. The errors were less than 2° .
  • the water droplets on these dual-scaled modified surfaces readily sit on the apex of the nanostructures, since air fills the space of the microstructures under a water droplet.
  • a water droplet on these dual-scaled modified surfaces can not penetrate into the surface.
  • the nano-scale pillars dramatically reduce the contact area between the water droplet and the solid surface. This exhibits the superhydrophobic property.

Claims (6)

  1. Procédé de préparation d'une surface hydrophobe, comportant les étapes suivantes :
    - diriger une buse de projection d'un appareil de projection de particules vers une surface d'un corps métallique ;
    - faire fonctionner l'appareil de projection de particules pour former, à la surface du corps métallique, des bosses et des creux à l'échelle micrométrique, par projection de particules sur la surface du corps métallique ;
    - former de multiples trous à l'échelle nanométrique sur la surface du corps métallique, en faisant subir au corps métallique un traitement d'oxydation anodique ;
    - former une réplique par immersion du corps métallique dans un matériau polymère non-mouillant et solidification de ce matériau polymère non-mouillant ;
    - et former une structure de surface super-hydrophobe à double échelle, comportant des nano-piliers formés sur les micro-bosses et micro-creux, en séparant de la réplique le corps métallique et l'oxyde d'anodisation.
  2. Procédé conforme à la revendication 1, dans lequel les particules utilisées dans l'appareil de projection de particules ont de 50 µm à 180 µm de diamètre.
  3. Procédé conforme à la revendication 1, dans lequel le matériau polymère non-mouillant est choisi dans l'ensemble constitué par les PTFE (polytétrafluoroéthylène), FEP (copolymères fluorés d'éthylène et de propylène) et PFA (perfluoroalcoxy-alcanes), ainsi que leurs combinaisons.
  4. Procédé conforme à la revendication 1, dans lequel le corps métallique est en aluminium ou en un alliage d'aluminium.
  5. Procédé conforme à la revendication 1, dans lequel l'appareil de projection de particules est une sableuse qui projette des particules de sable.
  6. Procédé conforme à la revendication 1, dans lequel l'appareil de projection de particules est conçu pour projeter des particules métalliques.
EP07768622.8A 2006-07-05 2007-07-05 Procédé destiné à la fabrication d'une surface superhydrophobe Not-in-force EP2038452B1 (fr)

Applications Claiming Priority (2)

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KR20060063101 2006-07-05
PCT/KR2007/003276 WO2008004828A1 (fr) 2006-07-05 2007-07-05 Procédé destiné à la fabrication d'une surface superhydrophobe et solide possédant une structure de surface superhydrophobe obtenue à l'aide dudit procédé

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EP2038452A1 EP2038452A1 (fr) 2009-03-25
EP2038452A4 EP2038452A4 (fr) 2012-10-03
EP2038452B1 true EP2038452B1 (fr) 2016-05-18

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US (1) US20100028615A1 (fr)
EP (1) EP2038452B1 (fr)
JP (1) JP5006394B2 (fr)
KR (1) KR100889619B1 (fr)
CN (1) CN101484612B (fr)
WO (1) WO2008004828A1 (fr)

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EP2038452A1 (fr) 2009-03-25
CN101484612B (zh) 2011-06-15
EP2038452A4 (fr) 2012-10-03
CN101484612A (zh) 2009-07-15
WO2008004828A1 (fr) 2008-01-10
US20100028615A1 (en) 2010-02-04

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